CN111690189B - Carboxyl nitrile rubber/carboxyl starch composite material and preparation method and application thereof - Google Patents
Carboxyl nitrile rubber/carboxyl starch composite material and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L13/00—Compositions of rubbers containing carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a carboxyl nitrile rubber/carboxyl starch composite material and a preparation method and application thereof. The preparation method has the advantages of simple and convenient processing process and macro-preparation process, environmental protection, sustainable development and environmental protection. The carboxyl nitrile rubber/carboxyl starch composite material has the advantages of high extensibility, high mechanical property and repeatable thermoplastic processing. The invention also discloses the application of the carboxyl nitrile rubber/carboxyl starch composite material in the fields of medical protection and food packaging.
Description
Technical Field
The invention belongs to the technical field of modified carboxyl nitrile rubber, and particularly relates to a carboxyl nitrile rubber/carboxyl starch composite material as well as a preparation method and application thereof.
Background
The carboxyl nitrile rubber (XNBR) is a novel synthetic rubber prepared by introducing acrylic acid and derivative monomers thereof in a certain proportion on the molecular chain of the nitrile rubber (NBR) in the free radical polymerization process. The introduction of carboxyl groups into nitrile rubbers improves their tensile strength, tear strength, hardness, abrasion resistance, adhesion and ozone aging resistance, in particular significantly increases their tensile strength at elevated temperatures. In addition, the carboxyl is introduced, so that the polarity of nitrile rubber molecules can be improved, the compatibility with polyvinyl chloride, phenolic resin and the like is increased, and the blended rubber with high hardness and excellent performances of wear resistance, oil resistance, chemical corrosion resistance, ozone aging resistance and the like can be obtained. The carboxyl nitrile rubber (XNBR) is widely used for producing various high-pressure sealing elements, oil-resistant rubber elements, high-wear-resistance sealing elements, rubber rollers, adhesives and other fields, and can also be used together with nitrile rubber (NBR), Chloroprene Rubber (CR) or other general diene rubbers for improving the wear resistance and the oil resistance of the rubbers. However, the carboxyl nitrile rubber (XNBR) has poor flexibility at low temperature, larger compression set and particularly poor scorch safety, and seriously influences the further application of the carboxyl nitrile rubber (XNBR). In the process of preparing the carboxyl nitrile rubber (XNBR), the existence of carboxyl and unsaturated double bonds endows the carboxyl nitrile rubber (XNBR) with the irreversible covalent crosslinking at the position of the double bonds by adopting a sulfur powder-accelerator or a peroxide vulcanization system like the common nitrile rubber (NBR), and the carboxyl can also react with metal oxide or salt thereof to form ionic reversible crosslinking bonds. The introduction of the ionic bond has obvious reinforcing and hardening effects on the whole macromolecular network, thereby improving the mechanical, thermal, solvent-resistant and other properties of the carboxyl nitrile rubber (XNBR) and greatly expanding the application field of the XNBR. Unfortunately, the stability of the ionomer networks is poor, the increase in the degree of ionic aggregation and phase separation increases the compression set of the compounds and the stress relaxation rate at high temperatures is increased, so that the properties of carboxylated nitrile rubber (XNBR) vulcanizates obtained by ionic crosslinking have not yet met the practical requirements [ L.Ibarra, A.Marcos-Fern & ltz & gt, M.Alzorriz. mechanical adaptation to the curing of carboxylated nitrile rubber (XNBR) by zinc peroxide/zinc oxide polymer,2002,43(5): 1649-.
The starch has wide sources, low price and good biodegradation and biocompatibility, and when the starch is blended with the carboxylated nitrile butadiene rubber (XNBR), the mechanical property, the thermal property, the barrier property and other properties of the biomass material can be further improved, and the cost of the biomass material can be reduced. The starch/carboxyl-butyl rubber, starch/natural rubber and other composite materials prepared by comparing an emulsion coprecipitation method and a mechanical blending method are also passed through. The addition of the starch granules can play a role in obviously enhancing the carboxyl nitrile rubber. [ Royafei, preparation, structure and performance of starch/nitrile rubber composite material [ D ], Beijing university of chemical industry, 2009 ]. Dauda et al, which uses natural sago starch as raw material and sulfuric acid as hydrolytic agent, the particle diameter of acidolysis starch is reduced from 1.233 μm to 0.313 μm, and its addition effectively improves the mechanical, biodegradation and anti-swelling properties of carboxylated nitrile butadiene rubber (XNBR), but the extensibility of carboxylated nitrile butadiene rubber (XNBR) decreases with the increase of starch content.
Through the analysis of domestic and foreign documents and patents for the preparation of the carboxyl nitrile rubber and starch composite material, the fact that the starch and the carboxyl nitrile rubber (XNBR) are blended to prepare the composite material is found that the variety of the used chemical reagents is large, the interface of the composite material is obviously separated along with the increase of the content of the starch, and the barrier property, the ductility and the thermal property of the composite material are reduced, so that the practical application is limited. The addition of curing and accelerators such as sulfur and dicumyl peroxide, while improving the tensile strength of carboxylated nitrile rubber (XNBR), also causes the disadvantages of difficult recycling and re-processing, resulting in a large amount of non-degradable rubber preparation.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide the preparation method of the carboxyl nitrile rubber/carboxyl starch composite material, and the preparation method has the advantages of simple and convenient processing process and macro-preparation process, environmental protection, sustainable development, environmental protection and the like.
The second purpose of the invention is to provide a carboxyl nitrile rubber/carboxyl starch composite material which has the advantages of high extensibility, high mechanical property and repeatable thermoplastic processing.
The third purpose of the invention is to provide the application of the carboxyl nitrile rubber/carboxyl starch composite material in the fields of medical protection and food packaging, and the application realizes the application of the carboxyl starch in the fields of the carboxyl nitrile rubber composite material with high mechanical property and barrier property, thereby expanding the application field of the non-edible starch.
The first purpose of the invention can be achieved by adopting the following technical scheme:
a preparation method of a carboxyl nitrile rubber/carboxyl starch composite material comprises the following steps:
(1) preparation of carboxyl starch: adding 30% of hydrogen peroxide and anhydrous copper sulfate into the gelatinized starch, and performing catalytic oxidation to obtain carboxyl starch;
(2) preparing a carboxyl nitrile rubber/carboxyl starch composite material: preparing the carboxyl starch in the step (1) into a suspension with the mass concentration of 10-40%, adding the carboxyl nitrile rubber emulsion into the carboxyl starch suspension, and stirring/drying to obtain a premix; and adding zinc oxide into the premix, carrying out open milling, and then carrying out hot pressing reaction and forming to obtain the carboxyl nitrile rubber/carboxyl starch composite material.
Preferably, the starch in step (1): 30% hydrogen peroxide: the mass ratio of the anhydrous copper sulfate is 500: 176-704: 0.15 to 0.35; the carboxyl starch in the step (2): carboxyl nitrile rubber: the mass ratio of zinc oxide is 30-50: 342-2000: 10 to 15.
Further preferably, the starch in step (1): 30% hydrogen peroxide: the mass ratio of the anhydrous copper sulfate is 500: 704: 0.35; the carboxyl starch in the step (2): carboxyl nitrile rubber: the mass ratio of the zinc oxide is 30: 342: 15.
preferably, the starch gelatinization in the step (1) specifically comprises the steps of mixing starch and deionized water according to the mass ratio of 500: 2200-2500, uniformly stirring, placing the mixed starch aqueous solution into a microwave oven for gelatinization, and cooling to room temperature.
Preferably, the carboxyl content of the carboxyl starch in the step (2) is 5% -100%, and the mesh number is 50-300 meshes.
Preferably, in the step (2), the solid content of the carboxylated nitrile-butadiene rubber emulsion is 20-45%, and the carboxyl content is 2.5-20%.
Preferably, the processing temperature of the hot-pressing reaction in the step (2) is 130-150 ℃, the reaction time is 15-50 min, and the pressure is 5-15 MPa.
Preferably, the particle diameter of the zinc oxide is 30-50 nm.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts metal oxides such as zinc oxide and the like as interface reactants, introduces carboxyl starch through the action of ionic bond, and uses Zn between carboxyl nitrile rubber (XNBR) and carboxyl starch (OST)2+For the strong phase acting force formed by ionic bonds, a carboxyl nitrile rubber/carboxyl starch composite material with good phase homogeneity is constructed between carboxyl nitrile rubber (XNBR) and starch, so that the mechanical, thermal and biological compatibility properties of the composite material are improved; the method has the advantages of environmental protection, simple preparation process, low cost, simple components and the like, and provides a new technical invention method for preparing and applying the high-performance recyclable thermoplastic carboxylic nitrile rubber.
2. Compared with the traditional preparation of the carboxylated nitrile rubber (/ starch composite material, the carboxylated nitrile rubber/carboxyl starch composite material prepared by the method has the characteristics of simple chemical components, environmental protection and good biocompatibility, and has good reversible physical cross-linking network and phase interface fusion formed based on the function of zinc ionic bonds, so that the material has the advantages of good repeatable thermoplastic processing performance, mechanical property, barrier property and the like, the impact strength is hinge damage free, the tensile strength can reach 10.0MPa, the fracture elongation is more than 800%, and the material has wide application prospects in the fields of food packaging contact materials, medical protective materials and the like.
3. The invention (1) has high mechanical property and can be repeatedly processed by hot molding: after adding zinc oxide, hydroxyl groups on the carboxyl starch (OST) and the carboxyl nitrile rubber (XNBR) react with zinc oxide (ZnO) to form ionic bonds in the conventional hot pressing process at normal temperature, pressure and the like, and when the addition amounts of the carboxyl starch (OST) and the zinc oxide (ZnO) are respectively 5-20 parts and 3-12 parts, the impact strength and the tensile strength of the carboxyl nitrile rubber/carboxyl starch composite material are greatly improved compared with those of the carboxyl nitrile rubber (XNBR). The ionic bonds are reversible, and the formed physically cross-linked network structure is broken at high temperature to exhibit thermoplasticity. (2) High thermal performance: the carboxyl group of the carboxyl nitrile rubber/carboxyl starch has strong ionic bond with zinc ions, so that the acting force of a molecular chain is increased, the thermal property of the material can be obviously improved, and the glass transition temperature can be increased by about 15 ℃. The material has wider temperature-resistant application range. (3) Green environmental protection and biodegradability: the invention takes carboxyl starch (OST) and carboxyl nitrile rubber (XNBR) as raw materials, zinc oxide (ZnO) as modified filler, has the advantages of simple components, low price, easy control of operation, no toxicity, no pollution and the like, and when the composite material is used for a plurality of times in a waste compost environment, the carboxyl nitrile rubber/carboxyl starch composite material can be promoted to carry out biodegradation due to the existence of the carboxyl starch (OST), thereby protecting the environment.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a graph of dynamic torque analysis of carboxylated nitrile rubber/carboxylated starch prepared in comparative examples 1 to 3 and in example 4;
FIG. 2 is an infrared spectrum of a carboxylated nitrile rubber/carboxylated starch prepared in comparative examples 1 to 3 and in example 4;
FIG. 3 is a DMA map of the carboxylated nitrile rubber/carboxylated starch prepared in comparative examples 1 to 3 and example 4, wherein (a) is the loss tangent (tan. delta.);
FIG. 4 is a DMA map of the carboxylated nitrile rubber/carboxylated starch prepared in comparative examples 1 to 3 and example 4, wherein (b) is the storage modulus;
FIG. 5 is an SEM photograph of the carboxylated nitrile rubber/carboxylated starch prepared in comparative example 1;
FIG. 6 is an SEM photograph of the carboxylated nitrile rubber/carboxylated starch prepared in comparative example 2;
FIG. 7 is an SEM photograph of the carboxylated nitrile rubber/carboxylated starch prepared in comparative example 3;
FIG. 8 is an SEM photograph of carboxylated nitrile rubber/carboxylated starch prepared by example 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions in the embodiments of the present invention will be described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
500g of starch is dissolved in 2500g of deionized water, then the starch and the deionized water are uniformly mixed under the mechanical stirring of 1000r/min, the mixed starch water solution is placed into a microwave oven for gelatinization treatment, and the mixture is cooled to room temperature. 352g of hydrogen peroxide solution with the mass fraction of 30 percent is added, 200 mg of anhydrous copper sulfate is added as a catalyst, the mixture reacts for 24 hours at the constant temperature of 35 ℃, the obtained carboxyl starch (OST) paste is placed in a blast oven at the temperature of 60 ℃, the carboxyl starch (OST) is dried to the constant weight, and the mixture is crushed into 200-mesh powder for standby. Weighing 50g of carboxyl starch (OST) powder, adding 300g of water, pouring into 2000g of carboxyl nitrile butadiene rubber (XNBR) emulsion with the solid content of 40%, mechanically stirring for 40 minutes (1000r/min), pouring into a stainless steel plate, and putting into a 60 ℃ blast oven to bake for 2 hours. And then carrying out open milling treatment on the mixture in an open mill, simultaneously adding 12g of zinc oxide with the particle diameter of 30nm, carrying out open milling for 35 minutes to obtain a sample, carrying out plate pressing treatment on the obtained sample in a flat vulcanizing machine, wherein the processing temperature is 135 ℃, the reaction time is 15 minutes, and the pressure is 7.5MPa, cutting the obtained sample into a standard test sample, and carrying out mechanical and thermal performance tests, wherein the test results are shown in Table 1.
Example 2
500g of starch is dissolved in 2500g of deionized water, then the starch and the deionized water are uniformly mixed under the mechanical stirring of 1000r/min, the mixed starch water solution is placed into a microwave oven for gelatinization treatment, and the mixture is cooled to room temperature. Adding 176g of hydrogen peroxide solution with the mass fraction of 30 percent, simultaneously adding 150 mg of anhydrous copper sulfate as a catalyst, reacting at the constant temperature of 35 ℃ for 36 hours, then placing the carboxyl starch (OST) paste into a blast oven at the temperature of 60 ℃, drying the carboxyl starch (OST) to constant weight, and crushing the starch to 200 meshes of powder for later use. 35g of carboxyl starch (OST) powder is weighed, 200g of water is added, 350g of carboxyl nitrile rubber (XNBR) emulsion with the solid content of 40% is poured into the mixture, mechanical stirring is carried out for 50 minutes (1000r/min), and the mixture is poured into a stainless steel plate and is put into a 65 ℃ forced air oven to be dried for 2.5 hours. And then carrying out open milling treatment on the mixture in an open mill, simultaneously adding 14g of zinc oxide with the particle diameter of 40nm, carrying out plate pressing treatment on the obtained sample in a plate vulcanizing press after the open milling time is 45 minutes, wherein the processing temperature is 145 ℃, the reaction time is 20 minutes, and the pressure is 9.5MPa, cutting the obtained sample into standard test samples, and carrying out mechanical and thermal property tests, wherein the test results are shown in Table 1.
Example 3
500g of starch is dissolved in 2200g of deionized water, then the starch and the deionized water are uniformly mixed under the mechanical stirring of 1000r/min, the mixed starch water solution is placed into a microwave oven for gelatinization treatment, and the mixture is cooled to room temperature. Adding 528g of hydrogen peroxide solution with the mass fraction of 30 percent, adding 350 mg of anhydrous copper sulfate as a catalyst, reacting at the constant temperature of 35 ℃ for 40 hours, placing the carboxyl starch (OST) paste in a blast oven at the temperature of 60 ℃, drying the carboxyl starch (OST) to constant weight, and crushing to 200-mesh powder for later use. 30g of carboxyl starch (OST) powder is weighed, 150g of water is added, 342g of carboxyl nitrile rubber (XNBR) emulsion with the solid content of 40% is poured into the powder, mechanical stirring is carried out for 45 minutes (1000r/min), and the powder is poured into a stainless steel plate and is put into a 65 ℃ forced air oven to be dried for 2 hours. Then, the mixture is subjected to open milling treatment in an open mill, 10g of zinc oxide with the particle diameter of 30nm is added, after the open milling time is 40 minutes, the obtained sample is subjected to plate pressing treatment in a flat vulcanizing press, the processing temperature is 150 ℃, the reaction time is 22 minutes, and the pressure is 8.0MPa, the obtained sample is cut into standard test samples, and the mechanical and thermal performance tests are carried out, wherein the test results are shown in Table 1.
Example 4
500g of starch is dissolved in 2200g of deionized water, then the starch and the deionized water are uniformly mixed under the mechanical stirring of 1000r/min, the mixed starch water solution is placed into a microwave oven for gelatinization treatment, and the mixture is cooled to room temperature. Adding 704g of 30% hydrogen peroxide solution by mass fraction, simultaneously adding 250 mg of anhydrous copper sulfate as a catalyst, reacting at the constant temperature of 35 ℃ for 48 hours, then placing the carboxyl starch (OST) paste in a blast oven at the temperature of 60 ℃, drying the carboxyl starch (OST) to constant weight, and crushing to 200-mesh powder for later use. 30g of carboxyl starch (OST) powder is weighed, 150g of water is added, 342g of carboxyl nitrile rubber (XNBR) emulsion with the solid content of 40% is poured into the mixture, mechanical stirring is carried out for 45 minutes (1000r/min), and the mixture is poured into a stainless steel plate and put into a 65 ℃ forced air oven to be dried for 2 hours. And then carrying out open milling treatment on the mixture in an open mill, simultaneously adding 15g of zinc oxide with the particle diameter of 50nm, carrying out plate pressing treatment on the obtained sample in a plate vulcanizing press after the open milling time is 30 minutes, wherein the processing temperature is 150 ℃, the reaction time is 20 minutes, and the pressure is 8.0MPa, cutting the obtained sample into standard test samples, and carrying out mechanical and thermal property tests, wherein the test results are shown in a figure 1 to a figure 8 and shown in a table 1.
Comparative example 1
342g of carboxylated nitrile rubber (XNBR) emulsion with a solid content of 40 percent is stirred mechanically (1000r/min) for 45 minutes and then poured into a stainless steel plate and put into a 65 ℃ blast oven to be dried for 2 hours. Then carrying out open milling treatment in an open mill, simultaneously adding 15g of zinc oxide with the particle diameter of 50nm, after the open milling time is 30 minutes, carrying out plate pressing treatment on the obtained sample in a flat vulcanizing press, wherein the processing temperature is 150 ℃, the reaction time is 20 minutes, and the pressure is 8.0MPa, cutting the obtained sample into a standard test sample, and carrying out mechanical and thermal performance tests, wherein the test results are shown in figures 1 to 8 and table 1.
Comparative example 2
500g of starch is dissolved in 2200g of deionized water, then the starch and the deionized water are uniformly mixed under the mechanical stirring of 1000r/min, the mixed starch water solution is placed into a microwave oven for gelatinization treatment, and the mixture is cooled to room temperature. The mixture is dried in a blast oven at 60 ℃ to constant weight and is crushed into 200-mesh powder for later use. Weighing 30g of starch powder, adding 150g of water, pouring 342g of carboxylated nitrile butadiene rubber (XNBR) emulsion with the solid content of 40%, mechanically stirring for 45 minutes (1000r/min), pouring into a stainless steel plate, and putting into a 65 ℃ forced air oven to be dried for 2 hours. And then carrying out open milling treatment on the mixture in an open mill, simultaneously adding 15g of zinc oxide with the particle diameter of 50nm, carrying out plate pressing treatment on the obtained sample in a plate vulcanizing press after the open milling time is 30 minutes, wherein the processing temperature is 150 ℃, the reaction time is 20 minutes, and the pressure is 8.0MPa, cutting the obtained sample into a standard test sample, and carrying out mechanical and thermal property tests, wherein the test results are shown in figures 1 to 8 and table 1.
Comparative example 3
500g of starch is dissolved in 2200g of deionized water, then the starch and the deionized water are uniformly mixed under the mechanical stirring of 1000r/min, the mixed starch water solution is placed into a microwave oven for gelatinization treatment, and the mixture is cooled to room temperature. Adding 704g of 30% hydrogen peroxide solution by mass fraction, adding 250 mg of anhydrous copper sulfate as a catalyst, reacting at the constant temperature of 35 ℃ for 48 hours, placing the mixture in a blast oven at the temperature of 60 ℃, drying the carboxyl starch (OST) to constant weight, and crushing to 200-mesh powder for later use. 30g of carboxyl starch (OST) powder is weighed, 150g of water is added, 342g of carboxyl nitrile rubber (XNBR) emulsion with the solid content of 40% is poured into the mixture, mechanical stirring is carried out for 45 minutes (1000r/min), and the mixture is poured into a stainless steel plate and put into a 65 ℃ forced air oven to be dried for 2 hours. And then carrying out open milling treatment on the mixture in an open mill for 30 minutes, then carrying out plate pressing treatment on the obtained sample in a plate vulcanizing press, wherein the processing temperature is 150 ℃, the reaction time is 20 minutes, and the pressure is 8.0MPa, the obtained sample is cut into standard test samples, and mechanical and thermal performance tests are carried out, and the test results are shown in figures 1 to 8 and table 1.
Fig. 1 to 8 show that the samples of the above example 4 and comparative examples 1 to 3 are tested by analysis means such as dynamic torque analysis, infrared spectroscopy, electron microscopy and dynamic mechanical mechanics, and the above experiments prove that zinc ions can react with carboxylated nitrile rubber (XNBR) and carboxylated starch (OST) at the same time, and the formed zinc salt has a physical crosslinking effect and can be tightly combined to form a thermodynamically stable homogeneous phase.
FIG. 1 is a graph showing the vulcanization profile of the carboxylated nitrile rubbers/carboxylated starches prepared in comparative examples 1 to 3 and in example 4. As can be seen from fig. 1, the ionic bond formed by the carboxylated nitrile rubber/carboxylated starch has a physical crosslinking effect by using zinc oxide (ZnO) as a reactant, and can significantly improve the torque thereof, which is a strong evidence for the reaction.
FIG. 2 is an infrared spectrum of a carboxylated nitrile rubber/carboxylated starch prepared in comparative examples 1 to 3 and example 4. As can be seen from FIG. 2, the use of zinc oxide (ZnO) enables simultaneous reaction with carboxylated nitrile rubber (XNBR) and carboxylated starch (OST), so that carboxylated nitrile rubber (XNBR) and carboxylated starch (OST) are at 1730cm-1C ═ O vibration absorption peak ascribed to carboxyl group disappeared, and ionic bond [ O-C ═ O ] formed]2The Zn absorption peak appears at 1595cm-1Position, consistent with the dynamic torque analysis curve, further verifiesStrong evidence for the formation of ionic salts is the neutralization of zinc oxide (ZnO) with carboxyl groups.
FIGS. 3 and 4 are DMA diagrams of the carboxylated nitrile rubbers/carboxylated starches obtained in comparative examples 1 to 3 and example 4, respectively, wherein (a) is the loss tangent (tan. delta.); (b) is the storage modulus. As can be seen from the figure, the glass transition temperature of the carboxylated nitrile rubber/the carboxylated starch is increased by-2.2 ℃ from-18.1 ℃, and further, the ionic bond formed by the carboxylated nitrile rubber/the carboxylated starch has a physical crosslinking effect, and the molecular chain movement of the carboxylated nitrile rubber (XNBR) is inhibited, so that the glass transition temperature is increased.
FIGS. 5 to 8 are SEM images of the carboxylated nitrile rubbers/carboxylated starches prepared in comparative examples 1 to 3 and example 4, respectively. As can be seen from the comparison graph, in the system of the carboxyl starch (OST) and the carboxyl nitrile rubber (XNBR), the carboxyl starch (OST) is embedded in the matrix of the carboxyl nitrile rubber (XNBR) in a chemical bond structure, but is not exposed on the surface of the carboxyl nitrile rubber (XNBR) in a pure particle form, so that the good interface compatibility is realized, and the result is consistent with the result of a DMA test.
Table 1 shows the mechanical property data of each of the samples of comparative examples 1 to 3 and examples 1 to 4
As can be seen from the examination of the tensile strength, the elongation at break and the notched impact strength of the samples of comparative examples 1 to 3 and examples 1 to 4, the tensile strength and the elongation at break of the samples of examples 1 to 4 are far superior to those of comparative examples 1 to 3. The data in table 1 show that the carboxylated nitrile rubber/carboxylated starch composite materials prepared in examples 1 to 4 have the advantages of good repeated thermoplastic processability, mechanical properties, barrier properties and the like, the impact strength is hinge damage-free, the tensile strength can reach 10.0MPa, and the fracture elongation is more than 800%.
The above description is only for the preferred embodiments of the present invention, but the protection scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the scope of the present invention.
Claims (10)
1. A preparation method of a carboxyl nitrile rubber/carboxyl starch composite material is characterized by comprising the following steps:
(1) preparation of carboxyl starch: adding 30% of hydrogen peroxide and anhydrous copper sulfate into the gelatinized starch, and performing catalytic oxidation to obtain carboxyl starch;
(2) preparing a carboxyl nitrile rubber/carboxyl starch composite material: preparing the carboxyl starch in the step (1) into a suspension with the mass concentration of 10-40%, adding the carboxyl nitrile rubber emulsion into the carboxyl starch suspension, and stirring/drying to obtain a premix; and adding zinc oxide into the premix, carrying out open milling, and then carrying out hot pressing reaction and forming to obtain the carboxyl nitrile rubber/carboxyl starch composite material.
2. The process for preparing a carboxylated nitrile rubber/carboxylated starch composite material according to claim 1, wherein in step (1) the ratio of starch: 30% hydrogen peroxide: the mass ratio of the anhydrous copper sulfate is 500: 176-704: 0.15 to 0.35; the carboxyl starch in the step (2): carboxyl nitrile rubber: the mass ratio of zinc oxide is 30-50: 342-2000: 10 to 15.
3. The process for preparing a carboxylated nitrile rubber/carboxylated starch composite material according to claim 2, wherein in step (1) the ratio of starch: 30% hydrogen peroxide: the mass ratio of the anhydrous copper sulfate is 500: 704: 0.35; the carboxyl starch in the step (2): carboxyl nitrile rubber: the mass ratio of the zinc oxide is 30: 342: 15.
4. the preparation method of the carboxylated nitrile rubber/carboxylated starch composite material according to any one of claims 1 to 3, wherein the starch gelatinization in the step (1) specifically comprises the steps of mixing starch and deionized water according to a mass ratio of 500: 2200-2500, uniformly stirring, placing the mixed starch aqueous solution into a microwave oven for gelatinization, and cooling to room temperature.
5. The method for preparing carboxylated nitrile rubber/carboxylated starch composite material according to any of the claims 1 to 3, wherein the carboxyl content of the carboxylated starch in step (2) is 5 to 100 percent, and the mesh number is 50 to 300.
6. The method for preparing the carboxylated nitrile rubber/carboxylated starch composite material according to any one of claims 1 to 3, wherein the solid content of the carboxylated nitrile rubber emulsion in the step (2) is 20 to 45 percent, and the carboxyl group content is 2.5 to 20 percent.
7. The preparation method of the carboxylated nitrile rubber/carboxylated starch composite material according to any one of claims 1 to 3, wherein the processing temperature of the hot-pressing reaction in the step (2) is 130 to 150 ℃, the reaction time is 15 to 50min, and the pressure is 5 to 15 MPa.
8. The method for preparing carboxylated nitrile rubber/carboxylated starch composite material according to any of the claims from 1 to 3, wherein the particle diameter of said zinc oxide is between 30 and 50 nm.
9. A carboxylated nitrile rubber/carboxylated starch composite material prepared according to the preparation process described in any one of claims 1 to 8.
10. Use of the carboxylated nitrile rubber/carboxylated starch composite material according to claim 9 in the fields of medical protection and food packaging.
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